Novel mercaptophenol derivatives

ABSTRACT

THERE ARE DESCRIBE NOVEL HYDROXYARYLTHIO ETHYLENE AND ETHANE DERIVATIVES CONTAINING IN THE POSITION B TO THE HYDROXYARYLTHIO RADICAL A CYANO, NITRO, AROMATIC, CARBONYL, SULFONYL, SULFINYL, PHOSPHINYL OR PHOSPHINOTHIOYL RADICAL. A PROCESS FOR THE PREPARATION OF SAID COMPOSITIONS, THEIR PESTICIDAL UTILITY AND PESTICIDAL CARBAMATE AND PHOSPHOROTHIOATE DERIVATIVES ARE ALSO DESCRIBED.

United States Patent Oice 3,636,074 Patented Jan. 18, 1972 US. Cl.260-470 17 Claims ABSTRACT OF THE DISCLOSURE There are described novelhydroxyarylthio ethylene and ethane derivatives containing in theposition to the hydroxyarylthio radical a cyano, nitro, aromatic,carbonyl, sulfonyl, sulfinyl, phosphinyl or phosphinothioyl radical. Aprocess for the preparation of said compositions, their pesticidalutility and pesticidal carbamate and phosphorothioate derivatives arealso described.

This invention relates to novel hydroxyarylthio compounds and a processfor preparing said compounds by the reaction of mercaptophenols withreactive unsaturated compounds.

The addition of mercaptans to olefins is well known. This reaction isdescribed by E. Emmet Reid in Organic Chemistry of Bivalent Sulfur, vol.11. Chemical Publishing Co., N.Y.C., 1960, pp. 29-34. Mercaptans addmore readily to unsaturated bonds adjacent to electron-accepting groupssuch as carbonyl. Unsaturated reagents of this type can be classed asMichael reaction acceptors. (The Michael :Reaction is described by E. O.Bergmann, O. Gensbury and R. Pappo in Organic Reactions, vol. 10, JohnWiley & Sons, New York, 1959). The scope of the reaction of mercaptansand these reactive unsaturated compounds encompasses a wide variety ofreagents as revealed in the literature. A few representative referencesinclude: C. D. Hurd and L. L. Gershhein (J. Am. Chem. Soc., 69,2328-2335, 1947) added mercaptans, including alkanethiols,mercaptoethanol, thiophenol, mercapto-substituted carboxylic acids andesters, and benzyl mercaptan to reactive olefins includingacrylonitrile, methyl acrylate, acrolein and crotonaldehyde; and F. B.Zienty, et al. (I. of Org. Chem, 31, 865-869, 1966) prepared adductsfrom ,B-morpholinoethanethiol and c p-unsaturated ketones, esters,nitriles and others.

The reactive unsaturated starting compounds of the present inventionenter into reactions with phenol. These reactants include a,3-unsaturated aldehydes, ketones, esters and sulfones. Aldehydes andketones give condensation products with phenol, such asphenolforrnaldehyde resins or 4,4-isopropylidene diphenol (bisphenol).Mercaptophenols having the hydroxyl and mercapto groups on adjacentcarbons form cyclic products with carbonyl compounds. Phenyl esters areformed by acetylation or transesterification of phenol with, forexample, citraconic anhydride, fumaryl chloride or ethyl acrylate.Phenol ethers are formed by the addition of a phenolic hydroxyl across areactive double bond; thus bis(2-phenoxyethyl) sulfone orB-phenoxycyanoethane are formed by the addition of phenol to divinylsulfone or acrylonitrile. As phenols are readily alkylated by olefins,mercaptophenol similarly could also be expected to become alkylated byolefins.

Mercaptophenol is not only a mercaptan, but it is also a phenol andtherefore has both a reactive hydroxyl group and a reactive ring. Onemight expect the above alternate reactions to take precedent over theaddition of the mercaptan group to an unsaturated bond. One could notpredict that the compounds of this invention would be produced by thereaction of a mercaptophenol and a reactive olefin or an acetylene.

In accordance with the present invention there are provided novelcompounds of the formulae:

(a) b is from zero to two inclusive and d is from zero to about six;

(b) provided that:

(1) when b is zero, X is selected from the group consisting of cyano,nitro and aromatic radicals;

(2) when b is one, X is selected from the group consisting of carbonyl,sulfonyl and sulfinyl;

(3) when b is two, X is selected from the group consisting of phosphinyland phosphinothioyl;

(c) R is from zero to about 20 carbon atoms and is selected from thegroup consisting of alkyl, aralkyl, alkaryl, aryl, carbalkoxy,carbaryloxy, alkoxy, aryloxy, alkylthio, arylthio, hydrogen, hydroxy,amino, cyano, carboxy,

H Y Y Jcs-A R 0H and -C=( it a it i (d) R is selected from the groupconsisting of R and CEC-Y6;

(e) Y and Y are independently selected from the group consisting ofhydrogen, halogen, alkyl, aralkyl and alkaryl of zero to about 20 carbonatoms;

(f) Y is selected from the group consisting of Y and 1SA(R OH, providedthat when Y is (g) Y is selected from the group consisting of Y and (h)Y is selected from the group consisting of Y and X(R)b (i) Y and Y areindependently selected from the group consisting of Y X(R) and S--A(ROH; provided that:

(1) when Y is SA(R OH, Y is X(R) and Y is hydrogen; (2) when Y is -SA(ROH, Y is hydrogen;

(j) R is of zero to about 20 carbon atoms and is selected from the groupconsisting of alkyl, aralkyl, alkaryl, aryl, carbalkoxy, carbaryloxy,alkoxy, aryloxy, alkylthio, arylthio, hydroxy, amino, mercapto, cyano,carboxy and halogen; and

(k) A is aryl of six to about 18 carbon atoms.

Also, in accordance with the present invention, there are provided aprocess for the preparation of said compositions, a pesticidal utilityand novel pesticidal derivatives.

The following list is illustrative of those compounds included withinthe scope of the present invention, additional such compounds beingdescribed in the working examples.

2- -hydroxyphenylthio) acrylonitrile 2- (4-hydroxyphenylthio)nitroethane diethyl Z-hydroxymethyl-Z- (4-hydroxyphenylthio vinylphosphate ethyl 2- (Z-hydroxy-3-chlorophenylthio vinyl ketone 4,5-diphenyl-4- 4-hydroxyphenylthio octane 2- 2,5 -dihydroxyphenylthiobutyric acid l-ethyl-1-(4-hydroxyphenylthio)maleimide 1,6-bis(Z-hydroxyphenylthio -3 ,4-hexanedione bis[2-chloro-2-(4-hydroxyphenylthio) ethyl] sulfoxide 3,5-dicyano-1,7-(bis(4-hydroxyphenylthio)heptane 2,2-bis (Z-hydroxyphenylthio) propionitrilephenyl 2- 3 -methyl-4-hydroxyphenylthio) propionate 1,1-bis(2-hydroxy-3,5-di-t-butylphenylthio) -3 -butanone tetracyano Z-hydroxy-S-chlorophenylthio ethane 2,6-dis 2-hydroxy-3 -t-butyl-S-methylphenylthio-2,6-

dimethyl-4-heptanone diethyl 2- Z-hydroxyphenylthio ethyl phosphonatetris (2-hydroxyphenylthioethyl phosphine oxide 2-( 2-nitrocyclohexylthio) phenol 2- (Z-hydroxyphenylthio butyraldehyde dimethyl1,2-bis (Z-hydroxyphenylthio) succinate 2-(2-hydroxyphenylthioethanesulfonic acid In the compositions of the present invention -X(R)is an activating group that promotes the addition reaction of amercaptophenol to an unsaturated carbon-carbon bond.

When X is an aromatic radical, it may contain up to about three fusedrings and may be carbocyclic or a heterocyclic ring containing nitrogen,sulfur or oxygen in addition to carbon. Typical examples of aromaticradicals are furyl, thienyl, pyridyl, phenyl, 'benzothienyl, quinoxalyl,naphthyl, anthryl and carbazyl.

When b is one, X is preferably sulfonyl or carbonyl. Preferably R isalkyl, aryl, alkoxy, aryloxy, amino or CHY CY Y S-A-(R OH, andpreferably R is from Zero to about ten carbon atoms.

A is preferably phenyl, and R a substituent on the aryl nucleus, A, ispreferably alkyl, aryl, halogen or hydroxy. When A is phenyl, d is fromzero to four, preferably from zero to two.

In the compositions of the present invention, Y, Y Y Y Y Y and Y arenoninterfering substituents and are preferably of zero to about tencarbon atoms. Y and Y are preferably hydrogen or alkyl, and Y, Y Y Y Y Yand Y are even more preferably hydrogen or alkyl.

When R or any one of the seven Y substituents is halogen, it may bechlorine, fluorine, bromine or iodine.

The unsaturated compounds that may be used as starting materials in thepreparation of the compounds of the present invention are of thefollowing formulae:

The subscript b and R Y, Y Y Y and X are as hereinbefore described.

In general said starting materials are described as a compoundcontaining the group, X(R adjacent to an unsaturated carbon-carbon bond.

(1) when b is zero and X is cyano:

l-cyanodecene-l, acrylonitrile, LZ-dicyanoethylene,

tetracyanoethylene, 3-cyanocyclohexane; (2) when I) is zero and X isnitro:

nitromalonaldehyde (the enol form), nitroethylene,

1 nitroisobutylene, (3 nitrostyrene, l-nitrocyclohexene,l-nitro-4-cyanobutene-1, and 1-chloro-3- nitro-Z-butene; (3) when b iszero and X is aromatic:

4-phenoxyvinylbenzene, phenylacetylene, styrene, fl-

chlorostyrene, 2 vinylpyridene, 2 (u-propenyl) pyridine,l-vinylnapthalene and 2-vinylthiophene; (4) when I) is one and X iscarbonyl:

acrolein, fi-ethoxyacrolein, crotonaldehyde, citral, cinnamaledehyde,phorone, methyl vinyl ketone, divinyl ketone, mesityl oxide, methylisopropenyl ketone, 2 benzylidenecyclohexanone, chalcone,furfurylideneacetophenone, carvone, isophorone, 2 methylcyclohexane 1,3dione (enol form), benzoyl acetone (enol form), 5-hydroxy-3-methyl-3-penten-2-one, methyl ethynyl ketone, 3-butyn- 2-one,5-hydroxy-3-pentene-2-one, phenyl propiolate, 4-nitrophenyl propiolate,benzyl propiolate,

diethyl acetylenedicarboxylate, dimethyl maleic :acid, dimethyl maleate,dioctyl fumarate, diphenyl itaconate, butyl acrylate, benzylmethacrylate, dodecyl cinnamate, dimethyl(2 hydroxyphenylthio)maleate,ethyl a-cyanocinnamate, S-methylthioacrylate,S-benzylmethylthioaceylate, acrylic acid, thioacrylic acid,propiolamide, acetylenedicarboxyamide, acrylamide; (5) when b is l and Xsulfinyl or sulfonyl:

ethylenesulfinic acid, ethylenesulfonic acid, methyl vinyl sulfoxide,divinyl sulfone, phenyl styryl sulfone, methyl ethylenesulfonate, phenyl3-propylenesulfonate, methyl ethylenesulfinate, ethylenesulfonic acid,N-ethylanilide: (6) when b is two and X is phosphinyl orphosphinothioyl:

dirnethyl vinyl phosphine oxide, vinyl diphenyl phosphine sulfide,diethyl vinylphosphonate, methyl methylvinylphosphinate and dimethylethynylphosphonate.

The starting mercaptophenol compositions of the present invention are ofthe formula: HS--A(R OH; wherein A, R and d are hereinbefore described.Said compositions may be prepared by methods known in the prior art orby the procedure described in copending ap plication Ser. No. 597,228,filed Nov. 28, 1966, now Pat. No. 3,468,961 granted on Sept. 23, 1969.

Two sets of reactions illustrate the processes for the preparation ofthe novel compositions of the present invention.

The starting compositions and novel compositions of the presentinvention are as hereinbefore described.

Although the reactions may be conducted in the absence of a solvent,they are normally conducted in the presence of a solvent. Typicalsolvents include benzene, toluene, xylene, heptane, hexane, chloroform,carbon tetrachloride, chlorobenzene, ethanol, t-butanol, acetic acid,dioxane, N,N-dimethylformamide, N-methyl-Z-pyrrolidone, tetrahydrofuranand dimethylsulfoxide.

Although the reactions may be conducted at a temperature of about zeroto about 200 degrees centigrade, the preferred temperature is from about10 to about degrees centigrade.

Although the reactions may be conducted in the absence of a catalyst,the time and temperature required to complete the reactions maygenerally be reduced by using a basic catalyst. Suitable catalystsinclude salts of strong bases and alcohols or weak acids, amines,quaternary amine bases and alkali or alkaline earth metals orhydroxides. Examples of catalyst are sodium methylate, sodium acetate,potassium carbonate, triethylamine, piperidine, triethylene diamine,trimethylbenzylammonium hydroxide, and sodium or magnesium metal andsodium hydroxide.

Pesticidal derivatives of the present invention are prepared by reactingthe compositions of the present invention with0,0-dialkylphosphorochloridothioate or alkyl isocyanates wherein thealkyl radical is of one to about five carbon atoms.

The compositions of the present invention and derivatives thereof areparticularly useful for the control of animal or plant pests. Theypossess certain insecticidal activity such as toxicity toward mites andthe like, bactericidal activity against Staphylococcus aureus and Xanthomonas phaseoli and the like.

Preparations containing the compositions of the present invention and/orderivatives thereof are conveniently made up as liquid or as solidformulations and as such they exhibit pesticidal activity. Examples ofsolid formulations are dusts, wettable powders, granules and pellets,which may contain a solid extender or carrier, such as sand, clays,tales, sawdust and the like. Where liquid formulations are desirable,liquid extenders, diluents, or carriers of a nonreactive nature aregenerally utilized, such as water, alcohols, glycols, petroleumdistillates, and the like.

The compounds of this invention are useful as pesticides and as chemicalintermediates. Because of unsaturation, the ethylene hydroxyarylthiocompositions of the present invention are especially useful asintermediates. By conventional hydrogenation or halogenation processesor by the process of the present invention, said compositions may beused as starting products for the preparation of the novel ethanehydroxyarylthio compositions of the present invention. All temperaturesare in degrees centigrade and all parts are by weight, unless otherwiseindicated.

EXAMPLE 1 To a solution of 13.0 parts of o-mercaptophenol and 0.4 partof triethylene diamine, 7.0 parts of methyl vinyl ketone were added. Theaddition takes place over a period of about minutes and during saidaddition the temperature rose to 50-60 degrees centigrade. Thetemperature was reduced to and maintained at degrees centigrade by meansof an ice bath. After an overnight storage, the reaction mixture wasfiltered. Concentration of the filtrate and recrystallization of theproduct from toluene resulted in the formation of 20.4 parts of product,representing a yield of 98%. The white crystalline product has a meltingpoint of 47-49 degrees centigrade. Found: C, 61.1%; H, 6.6%. Calculatedfor C H O S: C, 61.2 percent; H, 6.16 percent. The product wasidentified as having the formula:

are prepared in comparable yields by the reaction of methyl vinyl ketonewith m-mercaptophenol and p-mercaptophenol respectively.

EXAMPLE 2 To 19.5 parts (0.15 mole) of o-mercaptophenol, 0.7 part oftriethylenediamine and 15 parts of methyl methacrylate were added. Anexothermic reaction ensued. After stirring overnight, a light yellow oilwas isolated. Found:

S, 13.32 percent. Calculated for C H O S: S, 14.13-

percent. The compound was identified as having the formula EXAMPLE 3 To13.0 parts of o-mercaptophenol and 0.44 parts of triethylene diamine, 10parts of ethyl acrylate was added dropwise while the temperature wasmaintained at about -60 degrees centigrade with an ice bath. There wasobtained 23.6 parts of a pale yellow liquid. Found: S, 13.34 percent.Calculated for C H O S: 5, 14.16 percent.

The compound was identified as having the formula EXAMPLE 4 OH 41 H OHSCH2'CH2CCH3 f SCH-CH2COCH3 In a simllar manner, compositions of thefollowing (17:0 formulae: 50 H EXAMPLES 5-15 0 H H H CH In Examples 5-15the basic procedure specified in Ex- SC FC 3 50 ample 1 was followed,but different reactants were used, and as specified in Table I.

In Examples 16-34, the hydroxyarylthio compositions (I? and derivativesthereof were subjected to tests to determine whether they possesspesticidal activity. The following test methods were used.

TABLE I.ADDUCTS OF ORTHO-MERCAPTO PHENOL AND REACTIVE OLEFINSPercentages C. M.P. Calculated Found or Product Example Olefin B P./mm.,formula. 0 H S OH O H S OH 5 Ethylmaleate 136-140/003 014 5115058 56.366.08 10.75 5.69 56.25 6.11 10.7 5.69 6- Ethylfumarate" 14s-149 0.0501.11. 0 5 56.36 6.08 10.75 5.69 56.17 5.89 10.8 5.84 7- Butylacrylate116-119/0.01 CHHISOES 61.39 7.13 12.61 6.68 60.98 7.18 12.6 6.71 8Etl1ylmethacrylate 106/008 C12HuOaS 59.97 6.71 13.34 7.00 59.93 6.8913.4 7.13 9- Mesityloxido 55-57 015111.026 64.25 7.19 14.30 7.57 64.257.29 14.2 7.05 10-- Aerylamide 72-73 CDHIINOQS 54.82 5.58 16.26 8.6254.65 5.61 15.8 8.66 11 Acrylonitrile /006 CvHeNOS 60.31 5.06 17.89 9.4759.93 4.90 17.8 9. 34 12 Dimethylacetylene dicarboxylate 159.5-16L5 0181180682 54.81 4.60 16.3 43003.60) 54.60 4.75 15.8 4 14(8.60) 134-vinylpyridine 1435-1445 CHHIBNOS 67.50 5.66 13.86 67. 23 5.65 14.014.- Divinylsulfone 1598-1603 01 1 1 048 51.87 4.90 25.96 4.59(9.18)51.81 4.89 25.8 483(9.21)

Styrene 117-120/0.05 01.111408 72.8 6.1 13.9 4.35 71.3 5.9 14.5 4

1 Ethyl maleate and ethyl iumarate form the same adduct.

7 INSECTICIDE TEST Aphid test Ten-day-old Nasturtium plants wereinfested with black bean aphids (Aphz's iabae Scop.) so that the firsttwo leaves have from 50-100 aphids, sprayed with the chemical to betested, and caged in a piece of tubing which was coated with talcumpowder to prevent the escape of the aphids. Mortality was recorded bycounting the number of dead aphids.

Mite test Young pole lima bean plants (Sieva variety) were intested with50 to 100 adult mites (Tetranychus telarius L.) on both primary leaves,sprayed 24 hours thereafter with the chemical to be tested, and placedin the green house for from 24 to 48 hours, after which mortality wasrecorded by counting the number of dead mites.

Mexican bean beetle test Primary leaves of lime. bean plants wereexcised, dipped into a solution of the chemical to be tested, and dried.Then five larva (fourth instar) of the Mexican bean beetle (Epilachnavarivestis Muls.) were placed thereon, and the leaves were so enclosedthat the insects could not escape. Mortality was recorded by countingthe number of dead larvae, and the percent leaf consumed by the larvaewas estimated.

House fly test Newly hatched adult house flies (Musca domestica L.)were, while under the action of carbon dioxide, immersed in the chemicalsolution to be tested, shaken for a few seconds, and screened out into apaper cup containing filter paper which was dipped in sugar solution,said cups then being covered to prevent the escape of the flies. Tenflies were used per treatment. Data is taken on the number of fliesknocked down in two hours, and killed in 24 hours.

Bactericidal test The bacteria to be tested were grown on agar slantsfor hours. To a mixture of the chemical to be tested and nutrient agarwas added two drops of the bacterial suspension, and this mixture wasshaken and then poured onto sterilized Petri plates. The plates wereincubated for 24 hours, and the bacterial growth noted.

EXAMPLE 16 The hydroxyarylthio composition of the formula exhibitedcompleted control of the bacteria Staphylococcus aureus, Pseudomonasphaseolicola, and Xanthomonas phaseolz' at a concentration of 38 partsper million, and complete control of Escherichia coli at 86 parts permillion.

EXAMPLE 17 The hydroxyarylthio composition of the formula exhibitedcomplete control of the bacteria Staphylococcus aureus, at aconcentration of 255 parts per million and complete control ofPseudomonas phaseolicola at a concentration of 76 parts per million.

8 EXAMPLE 18 The hydroxyarylthio composition of the formula exhibitedcomplete control of the bacteria Staphylococcus aureus and Pseudomonasphaseolicola at a concentration of 38 parts per million and completecontrol of Xamhomonas phaseoli at 76 parts per million.

EXAMPLE 19 The hydroxyarylthio composition of the formula killed 80percent of the Mexican bean beetle at a concentration of 1000 parts permillion.

EXAMPLE 20 The hydroxyarylthio composition of the formula killed 40percent of the Mexican bean beetle at a concentration of 1000 parts permillion.

EXAMPLE 21 To 19.5 parts of o-mercaptophenol and 0.7 part oftriethylenediamine, 15 parts of methylmethacrylate were added. Afterstirring overnight, a light yellow oil was isolated. The product wasidentified as o-hydroxyphenyl Z-carbomcthoxypropyl sulfide, and 5 partsof it were dissolved in about 80 parts of methyl ethyl ketone. To theresulting solution, 8.6 parts of anhydrous potassium carbonate and 0.05part of powder copper were added. The mixture was heated at reflux forabout 30 minutes, and to it, 5.27 parts of 0,0-diethylphosphorochloridothioate was added over a 10 minute period. The mixturewas heated to reflux for about 2 hours, cooled and filtered. About fiveparts of 0,0-diethyl o-(2 (2-carbomethoxypropylthio)- phenyl)phosphorothioate was collected.

Said products of the formula i o-moouenn s-oPn-bH-cooon.

exhibited complete control of the bacteria Staphylococcus aurcus at aconcentration of 255 parts per million. At a concentration of 1000 partsper million percent of the Mexican bean beetles, 100 percent of themites and 94 percent of the aphids were killed. At a concentration ofparts per million 100 percent of the housefiies were knocked down aftertwo hours and 70 percent were killed at the end of 24 hours.

In Examples 22-28 phosphorothioate derivatives of the hydroxyarylthiocompositions of the present invention were prepared in a manner similarto Example 21 and were tested for pesticidal activity.

EXAMPLE 22 The phosphorothioate derivative of the formula at aconcentration of 1000 parts per million, killed 100 ercent of the mitesand knocked down 100 percent of the flies within two hours and killed100 percent of the houseflies in 24 hours.

EXAMPLE 23 The phosphorothioate derivative of the formula killed 100percent of the mites, knocked down 100 percent of the housefiies andkilled 100 percent of the houseflies at a concentration of 1000 partsper million.

EXAMPLE 24 The phosphorothioate derivative of the formula SCOOCH3GHQ-000cm killed 100 percent of the mites, knocked down 100 percent ofthe housefiies and killed 100 percent of the houseflies at aconcentration of 1000 parts per million.

EXAMPLE 25 The phosphorothioate derivative of the formula exhibitedcomplete control of the bacteria Staphylococcus aurcus, Pseudomonasphaseolicola and Xanthomonas phaseoli at a concentration of 255 partsper million.

EXAMPLE 27 The phosphorothioate derivative of the formula S O- l (OCH3)2exhibited complete control of the bacteria Pseudomonas phaseolz'cola ata concentration of 255 parts per million, killed 61 percent of aphids ata concentration of 1000 parts per million and killed 70 percent of theflies at a concentration of 1000 parts per million.

EXAMPLE 28 The phosphorothioate derivative of the formula killed 100percent of the housefiies at a concentration of 1000 parts per million.

The carbamate derivatives of the hydroxyarylthio compositions of thepresent invention in Examples 29-35 were prepared by adding about 5 toabout 10 parts of a composition of a hydroxyarylthio composition to asolution containing about 40 to about 60 parts benzene and about 5 to 10parts of methyl isocyanate. The benzene and excess methylisocyanate wereremoved under reduced pressure after about a 2 to 24 hour reactionperiod.

EXAMPLE 29 The carbamate derivative of the formula 0 0 ':NHCH;

killed 100 percent of the aphids and Mexican bean beetles at aconcentration of 1000 parts per million. Said compound knocked downpercent of the housefiies and killed percent of the housefiies at aconcentration of 1000 parts per million.

EXAMPLE 30 The carbamate derivative of the formula exhibited completecontrol of Pseudomonas phaseolicola and X anthomonas phaseoli at aconcentration of 255 parts per million. It killed percent of the aphidsand 60 percent of the Mexican bean beetles at a concentration of 1000parts per million and knocked down 80 percent and killed 60 percent ofthe housefiies at the same concentration.

EXAMPLE 31 The carbamate derivative of the formula exhibited completecontrol of Staphylococcus aureus, Pseudomonas phaseolicola, andXanthomonas phascoli at a concentration of 255 parts per million.

EXAMPLE 32 The carbamate derivative of the formula exhibited completecontrol of Staphylococcus aureus, Pseudomonas plzaseolicola, andXanthomonas phaseoli at a concentration of 255 parts per million andkilled 40 percent of the housefiies at a concentration of 1000 parts permillion.

EXAMPLE 33 The carbamate derivative of the formula killed 40 percent ofthe Mexican bean bettles at a concentration of 1000 parts per million.

1 1 EXAMPLE 34 The carbamate derivative of the formula I CH exhibitedcomplete control of Pscudomonas phaseolicola at a concentration of 255parts per million, and killed 53 percent of the aphids and 20 percent ofthe Mexican bean beetles at a concentration of 1000 parts per million.

While there have been described various embodiments of the presentinvention, the methods and compositions described are not intended to beunderstood as limiting the scope of the invention as it is realized thatchanges therein are possible. It is further intended that each elementrecited in any of the following claims is to be understood as referringto all equivalent elements for accomplishing substantially the sameresults in substantially the same or equivalent manner. It is intendedto cover the invention broadly in whatever form its principles may beutilized.

We claim:

1. A compound of the formula wherein d is zero to 2, inclusive;

R is independently selected from the group consisting of alkoxy of up to12 carbon atoms;

R is independently selected from the group consisting of lower alkyl,lower alkyl thio, lower alkoxy, hydroxy, halo and phenoxy;

Y is independently selected from the group consisting of hydrogen andlower alkyl;

Y and Y are independently selected from the group consisting of hydrogenand lower alkyl.

2. The compound of claim 1 wherein d is from zero to two, inclusive andY and Y are independently selected from the group consisting of hydrogenand lower alkyl.

3. The compound of claim 2 wherein R is alkoxy of up to 12 carbon atoms.

4. The compound of claim 2 wherein R is lower alkoxy.

5. The compound of claim 2 wherein d is zero.

6. The compound of claim 2 wherein d is l.

7. The compound of claim 2 wherein d is 2.

8. The compound of claim 2 wherein R is hydrogen.

9. The compound of claim 2 wherein R is lower alkyl. The compound ofclaim 2 wherein Y is hydrogen. The compound of claim 2 wherein Y ishydrogen. The compound of claim 2 wherein Y is hydrogen. The compound ofclaim 2 wherein Y is lower The compound of claim 2 wherein Y is lowerThe compound of claim 2 wherein Y is lower A compound of the structure17. A compound of the structure References Cited UNITED STATES PATENTS2,828,321 3/1958 Bullock 260470 2,828,322 3/1958 Bullock 2604703,468,961 9/1969 Geering et al. 260609 FOREIGN PATENTS 1,369,616 7/1964France 260-609 OTHER REFERENCES Chapman et al., J. Chem. Soc., vol. 30,pp. 1520-21, 1965.

ALAN L. ROTMAN, Primary Examiner U.S. Cl. X.R.

260250 R, 294.8 G, 294.9, 295 R, 295.5 R, 330.5, 332.2 A, 347.4, 465 F,479 C, 609 R, 942; 424250, 266, 274, 275 285, 300, 304

"H050 UNITED STATES PATENT OFFICE CERTIFICATE 6F COREC'HON Pate t N 3, 37 D t d January 18, l972 Inventor(s) Emil J= Geerinq and Norman w. DachsIt is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 2, line 27 (formula) I (I should read C I C line 62, "2(-hydroxyphenylthio)" should read --2--(2-hydroxypheny-lthio)-. Column3, line 6, "2,6-d1's" should read --?.,6 b1's; line 67,"cinnamaledehyde" should read -c1'nnamaldehyde--. Column l, line 6,"methylthioaceylate" should read methylthioacetylate--; line 35(Formula) S-A-(R should read S-A-(R OH OH Column 7, line 6l, "86 partsshould read ---76 parts---. Column l0, l ine l3, 0 should read 0 I llO-C- Column l2, line 20, C 0

II II n l: c2H 3 should read S'-CH --CH--COC H3 CH CH u H H ll line 27,S CH2 CH C O C H5 shoul d read S CH CH C 0 C H5 Signed and sealed this13th day of June 1972.

l (SEAL) J fittest:

EDWARD M FLETCHER, JR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents

